US4146723A - Heterocyclic diisocyanates and a process for making polyurethanes and polyurethane-ureas - Google Patents

Heterocyclic diisocyanates and a process for making polyurethanes and polyurethane-ureas Download PDF

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Publication number
US4146723A
US4146723A US05/457,290 US45729074A US4146723A US 4146723 A US4146723 A US 4146723A US 45729074 A US45729074 A US 45729074A US 4146723 A US4146723 A US 4146723A
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US
United States
Prior art keywords
radical
phenyl
formula
isocyanuric acid
reaction
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Expired - Lifetime
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US05/457,290
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English (en)
Inventor
Kurt Findeisen
Kuno Wagner
Erich Klauke
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Bayer AG
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Bayer AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/08—1,2,4-Thiadiazoles; Hydrogenated 1,2,4-thiadiazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/775—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7875—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/7887—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring having two nitrogen atoms in the ring

Definitions

  • This invention relates generally to organic diisocyanates and more particularly to heterocyclic diisocyanates and to a process for producing them.
  • Organic polyisocyanates are reacted with organic compounds having reactive hydrogen atoms determinable by the Zerewitinoff method to make non-porous and cellular polyurethanes.
  • the heretofore available polyisocyanates can be used advantageously in the manufacture of most polyurethanes but are not entirely suitable in some instances for making high temperature and chemical resistant foils and lacquers.
  • B represents a divalent organic radical
  • y represents a divalent radical containing one of the following sequences of atoms --C--C--; --C--S--; --C--N--C; or --S--N--C in the linear chain and n represents an integer of from 1 to 3.
  • B may in particular represent divalent aliphatic, cycloaliphatic, araliphatic or aromatic radicals or multi-nuclear aromatic radicals bridged by methylene, oxygen or sulphur groups; these radicals may be substituted one or more times with alkyl groups or alkoxy groups having one to six carbon atoms or with chlorine.
  • radicals represented by B alkylene radicals containing 5 or 6 carbon atoms such as C 5 H 10 -- and C 6 H 12 --, cycloalkylene radicals containing 5 or 6 carbon atoms such as C 5 H 8 -- and C 6 H 10 --, phenylene radicals, diphenylmethane radicals, diphenylether and diphenylthioether radicals which may be substituted one or more times with alkyl groups or alkoxy groups containing one to six carbon atoms such as methyl, ethyl, propyl, butyl, amyl, hexyl, methoxy, ethoxy, propoxy, butoxy, amoxy, hexoxy or chlorine.
  • radicals represented by y may be the radicals having the chains indicated above in which the free valencies of the carbon atoms are substituted with hydrogen, oxygen or nitrogen, the free valencies of the nitrogen atoms are subtituted with hydrogen or alkyl having one to six carbon atoms and the free valencies of the sulphur atoms are substituted with oxygen.
  • radicals y ##STR3##
  • the invention also provides a process for making heterocyclic diisocyanates of formula I above which is characterised in that a urea derivative of the formula ##STR4## in which B and n have the meanings indicated above are reacted with compounds of the formula
  • Hal represents halogen (preferably chlorine or fluorine), at temperatures of about 0° to about 200° C. and optionally in an inert organic diluent, the reaction being accompanied by ring closure.
  • the reaction is preferably carried out in the presence of a liquid organic diluent such as for example polar inert solvents having a boiling point of from about 30° to about 200° C. such as methylene chloride, o-dichlorobenzene, acetonitrile, chlorobenzene and the like as a reaction medium.
  • a liquid organic diluent such as for example polar inert solvents having a boiling point of from about 30° to about 200° C.
  • a liquid organic diluent such as for example polar inert solvents having a boiling point of from about 30° to about 200° C.
  • a liquid organic diluent such as for example polar inert solvents having a boiling point of from about 30° to about 200° C.
  • the urea diisocyanate of formula II need not be soluble in the diluent because the reaction may also be carried out in a heterogeneous phase.
  • the reaction is carried out within the temperature range of about 0° to about 200° C., preferably at about 20° to about 140° C. and more particularly at about 20° to about 60° C.
  • any suitable diluent which is non-reactive with the urea diisocyanate, the compound Hal--y--Hal or the resulting diisocyanate may be used such as for example, halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, dichloroethylene and trichloroethylene, halogenated aromatic compounds such as chlorobenzene, dichlorobenzene and trichlorobenzene as well as dioxane, ethyl acetate, acetone, acetonitrile, toluene, xylene and the like may be used.
  • halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, dichloroethylene and trichloroethylene
  • halogenated aromatic compounds such as chlorobenzene, dichlorobenzene and trichlorobenzene as well as dioxane, ethyl acetate, acetone, aceton
  • the reaction provided by the invention may be catalyzed with bases although it is generally not necessary to use a catalyst. In exceptional cases, tertiary bases are added to obtain a more rapid reaction.
  • Particularly suitable catalysts are triethylamine, diazabicyclo-(2,2,2)-octane, 1,5-diazabicyclo(4,3,0)-non-5-ene, I,8-diazabicyclo-(5,4,0)-undec-7-ene, dimethyl aniline, dimethyl benzylamine and pyridine.
  • Any urea diisocyanate of formula II may be used as the starting material.
  • Such ureas can be prepared easily by the process described in French Patent Specification No. 1,103,329.
  • ⁇ , ⁇ - and ⁇ , ⁇ -bifunctional compounds of the formula Hal-y-Hal used for ring closure are also already known (see e.g. DOS No. 1,768,179; DBP No. 1,224,720; synthesis, 1970, 542; DOS No. 1,932,830; DOS No. 2,013,433).
  • ⁇ , ⁇ - and ⁇ , ⁇ -bifunctional compounds (which corresponds to 1,2- and 1,3-bifunctional compounds) is therefore used in the context of this invention to denote substances which react under the given reaction conditions to split off at least one mol of hydrogen chloride.
  • ⁇ , ⁇ -bifunctional compounds oxalyl chloride, chloroacetyl chloride, perfluorodiaza-2,5-hexadiene-(2,4) and chlorocarbonyl-sulphenic acid chloride.
  • ⁇ , ⁇ -bifunctional compounds chlorocarbonyl isocyanate, bis-(chlorocarbonyl)-amines, chlorocarbonyl isocyanide dichloride and chlorosulphonyl isocyanate.
  • the isocyanate group is a particularly reactive substituent. It is therefore completely unexpected to find that urea diisocyanates can react with ⁇ , ⁇ - and ⁇ , ⁇ -bifunctional compounds to be converted into heterocyclic diisocyanates while yet preserving the isocyanato groups and without side reactions taking place to any substantial extent. It is all the more surprising since it has been disclosed in DOS No. 1,518,873 that oxalyl chloride reacts with isocyanates to form N-halogen-carbonyl-N-halogenoxyalkyl-amines.
  • urea diisocyanate of formula II is suspended in methylene chloride, and one mol of oxalyl chloride is then added. Hydrogen chloride starts to evolve within a short time and urea diisocyanate slowly dissolves. When all of the urea diisocyanate has completely dissolved, the reaction mixture is heated to 45° C. (reflux) for some time to complete the reaction. This reaction is illustrated by the following equation: ##STR5## n is an integer of 1 to 3.
  • the new heterocyclic diisocyanates provided by the invention are suitable for all the known applications of diisocyanates, for example low-molecular weight derivatives (urethanes, ureas, phosphorus derivatives, sulphur compounds etc.) may be used as pesticide for plant protection.
  • products which are suitable for use as coatings, as polyurethane elastomers and for producing molded products, including molded polyurethane foam products may be produced by the known methods of polyisocyanate polyaddition with one of the new diisocyanates.
  • the new heterocyclic diisocyanates are particularly important for producing temperature-resistant lacquers and foils.
  • High-molecular weight substances which are resistant to acid chemicals can be produced by controlled incorporation of the new heterocyclic diisocyanates and in particular of parabanic acid diisocyanate.
  • the new heterocyclic diisocyanates may also be used as mixtures, e.g. together with known polyisocyanates.
  • Polymers which contain parabanic acid residues and hydantoin residues are improved in their stabilitty to acids and have excellent resistance to high temperatures.
  • the reaction product may be purified by boiling with toluene, filtering and precipitating with cleaning petrol.
  • the solvent is distilled off and the residue is taken up with xylene which causes the triethylamine hydrochloride to precipitate while the desired reaction product remains in solution. After removal of the solvent by distillation, the desired reaction produce is left behind.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
US05/457,290 1973-04-11 1974-04-02 Heterocyclic diisocyanates and a process for making polyurethanes and polyurethane-ureas Expired - Lifetime US4146723A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2318170 1973-04-11
DE2318170A DE2318170A1 (de) 1973-04-11 1973-04-11 Heterocyclische diisocyanate

Publications (1)

Publication Number Publication Date
US4146723A true US4146723A (en) 1979-03-27

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US05/457,290 Expired - Lifetime US4146723A (en) 1973-04-11 1974-04-02 Heterocyclic diisocyanates and a process for making polyurethanes and polyurethane-ureas

Country Status (10)

Country Link
US (1) US4146723A (fr)
JP (1) JPS49135972A (fr)
BE (1) BE813419A (fr)
DE (1) DE2318170A1 (fr)
FR (1) FR2225426B1 (fr)
GB (1) GB1437846A (fr)
IE (1) IE39126B1 (fr)
IT (1) IT1015914B (fr)
LU (1) LU69820A1 (fr)
NL (1) NL7404774A (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4330453A (en) * 1980-09-29 1982-05-18 Exxon Research & Engineering Co. Polymers characterized by 1,3-imidazolidine-1,3-diyl rings plasticized with esters of aromatic carboxylic acids
US4332953A (en) * 1979-11-08 1982-06-01 Basf Wyandotte Corporation Carbamylbiuret-modified polyisocyanates
US4680195A (en) * 1984-05-17 1987-07-14 Ciba-Geigy Corporation Homopolymers, copolymers and coated material and its use
US4698295A (en) * 1984-11-16 1987-10-06 Ciba-Geigy Corporation Polyimides, a process for their preparation and their use, and tetracarboxylic acids and tetracarboxylic acid derivatives
US4898806A (en) * 1985-04-11 1990-02-06 Ciba-Geigy Corporation Coated material and use thereof
US5468835A (en) * 1994-04-20 1995-11-21 Caterpillar Inc. Polyetherpolyurethane end caps for oil filters
USH1928H (en) * 1998-05-11 2000-12-05 Caterpillar Inc. High viscosity, solvent resistant, thermoset polyetherpolyurethane and A process for making the same
US6479508B1 (en) 2000-07-06 2002-11-12 Boehringer Ingelheim (Canada) Ltd. Viral polymerase inhibitors

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2750771A1 (de) * 1977-11-12 1979-05-17 Bayer Ag Hydantoine
DE2750772A1 (de) * 1977-11-12 1979-05-17 Bayer Ag Heterocyclische polyisocyanate (iii)
DK529378A (da) * 1978-01-09 1979-07-10 Shell Int Research Anilidderivater
DE3018198A1 (de) * 1980-05-13 1981-11-19 Bayer Ag, 5090 Leverkusen Neue isocyanato-isocyanurate, ein verfahren zu ihrer herstellung, sowie ihre verwendung als isocyanat-komponente in polyurethan-lacken
AT375652B (de) * 1982-10-29 1984-08-27 Valentina Alexandro Postnikova Verfahren zur herstellung von arylaliphatischen polyisozyanuraten

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2514353A (en) * 1947-05-24 1950-07-04 Monsanto Chemicals Co 2-oxo-4, 5-diimino parabanic acid resins
US2526757A (en) * 1944-03-01 1950-10-24 Du Pont Preparation of ethyleneurea
US3410866A (en) * 1965-03-12 1968-11-12 Du Pont Isocyanates of selected fluoroalkylimidazolines
GB1302248A (fr) * 1969-03-27 1973-01-04
GB1303323A (fr) * 1969-04-15 1973-01-17
US3787435A (en) * 1970-12-18 1974-01-22 Bayer Ag 4,5-bis-(trifluoromethylimino)-diazoles
US3912754A (en) * 1973-06-08 1975-10-14 Bayer Ag Organic polyisocyanates and method of making them

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2526757A (en) * 1944-03-01 1950-10-24 Du Pont Preparation of ethyleneurea
US2514353A (en) * 1947-05-24 1950-07-04 Monsanto Chemicals Co 2-oxo-4, 5-diimino parabanic acid resins
US3410866A (en) * 1965-03-12 1968-11-12 Du Pont Isocyanates of selected fluoroalkylimidazolines
GB1302248A (fr) * 1969-03-27 1973-01-04
GB1303323A (fr) * 1969-04-15 1973-01-17
US3787435A (en) * 1970-12-18 1974-01-22 Bayer Ag 4,5-bis-(trifluoromethylimino)-diazoles
US3912754A (en) * 1973-06-08 1975-10-14 Bayer Ag Organic polyisocyanates and method of making them

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Chem. Abstracts 82:125981 v. *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4332953A (en) * 1979-11-08 1982-06-01 Basf Wyandotte Corporation Carbamylbiuret-modified polyisocyanates
US4330453A (en) * 1980-09-29 1982-05-18 Exxon Research & Engineering Co. Polymers characterized by 1,3-imidazolidine-1,3-diyl rings plasticized with esters of aromatic carboxylic acids
US4680195A (en) * 1984-05-17 1987-07-14 Ciba-Geigy Corporation Homopolymers, copolymers and coated material and its use
US4783372A (en) * 1984-05-17 1988-11-08 Ciba-Geigy Corporation Homopolymers, copolymers and coated material and its use
US4698295A (en) * 1984-11-16 1987-10-06 Ciba-Geigy Corporation Polyimides, a process for their preparation and their use, and tetracarboxylic acids and tetracarboxylic acid derivatives
US4898806A (en) * 1985-04-11 1990-02-06 Ciba-Geigy Corporation Coated material and use thereof
US5468835A (en) * 1994-04-20 1995-11-21 Caterpillar Inc. Polyetherpolyurethane end caps for oil filters
USH1928H (en) * 1998-05-11 2000-12-05 Caterpillar Inc. High viscosity, solvent resistant, thermoset polyetherpolyurethane and A process for making the same
US6479508B1 (en) 2000-07-06 2002-11-12 Boehringer Ingelheim (Canada) Ltd. Viral polymerase inhibitors

Also Published As

Publication number Publication date
DE2318170A1 (de) 1974-10-31
NL7404774A (fr) 1974-10-15
IE39126L (en) 1974-10-11
IE39126B1 (en) 1978-08-02
BE813419A (fr) 1974-10-08
FR2225426B1 (fr) 1978-06-02
JPS49135972A (fr) 1974-12-27
LU69820A1 (fr) 1974-11-21
IT1015914B (it) 1977-05-20
GB1437846A (en) 1976-06-03
FR2225426A1 (fr) 1974-11-08

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